Ashless oil additives

ABSTRACT

This invention concerns the condensation product of an aldehyde reactant having more than one carbon atom and/or ketone reactant, formaldehyde, an alkylene polyamine, and an alkyl-substituted phenol. These compositions can be used as ashless alkaline additives for lubricating oils.

United States Patent 1191 Traise et al.

ASHLESS 01L ADDITIVES Inventors: Thornton P. Traise, Chicago Heights;Roger W. Watson, Batavia, both of 111.; Randel Q. Little, Munster, Ind.

Assignee:

Filed: Oct. 15, 1970 Appl. No.: 81,190

Related U.S. Application Data Division of Ser. No. 774,497, Nov. 8,1968, Pat. No.

U.S. Cl ..260/583 P, 260/268 R, 260/5l.5, '260/239 A, 260/309.7, 260/593R, 260/601 R, 260/619 R, 260/624 R, 260/626 R, 260/626 T, 252/51.5 R

Int. Cl. ..C08g 9/04, C08g 9/26, C08g 9/34, C08g 37/24, C08g 37/18, C08g37/36 Field of Search ..260/296 R, 583 P, 51.5, 268 R; 252/5 1 .5 R

Standard Oil Company, Chicago, 111. I

Primary Examiner-Henry R. Jiles Assistant ExaminerRobert T. BondAttorney-Arthur G. Gilkes, William T. McClain and John J. Connors [57]ABSTRACT This invention concerns the condensation product of an aldehydereactant having more than one carbon atom and/0r ketone reactant,formaldehyde, an alkylene polyamine, and an alkyl-substituted phenol.These compositions can be used as ashless alkaline additives forlubricating oils.

3 Claims, No Drawings ASHLESS OIL ADDITIVES RELATED APPLICATIONS Thisapplication is a divisional of U.S. application Ser. No. 774,497, filedNov. 8, 1968 now U.S. Pat. No. 3,591,598 and entitled ASHLESS OILADDITIVES.

BACKGROUND OF THE INVENTION Known lubricating oils for engines developacidic materials which react with the oil to form sludge and varnishthat interfere with the operation of the engine. The addition ofalkaline additives to oils neutralizes the acidic materials, renderingthem harmless. Many conventional additives include metals, and thesemetalcontaining additives make their way into the combustion chamber ofthe engine and are burned, leaving an ash which hampers the performanceof the engine and which is occasionally blown from the exhaust asred-hot particles that can cause fires. Researchers, in attempting tofind ashless additives which are soluble or miscible in lubricating oiland which themselves do not harm engine parts, have investigated lowmolecular weight Mannich compounds. However, at effectiveconcentrations, many of these Mannich compounds are immiscible with orinsoluble in lubricating oils.

SUMMARY OF THE INVENTION We have discovered novel compositions whichserve an alkylene polyamine. The second method calls for reacting analdehyde reactant having more than one carbon atom, or a ketonereactant, or a mixture of said aldehyde and ketone reactants with analkylene polyamine to form an intermediate, and then reacting theintermediate with formaldehyde and an alkyl-substituted phenol. Thereactions are exothermic, but we usually heat the reaction mixture toatemperature between about 100 C and about 200 C, preferably betweenabout 110 C and about 180C. This additional heating drives the reactionsto substantial completion and removes water of condensation from theproduct.

The above-mentioned Mannich condensation product is a strong anti-acid.But, if it has a low molecular weight, it is not readily soluble in oil.We have found that these low molecular weight Mannich condensationproducts react with aldehydes and ketones to produce excellent alkalineadditives which are soluble or miscible in oil. Oils containing a minoramount of the alkaline additives of our invention, generally from about5 to about 20 weight percent, do not deleteriously affect engines and,in fact, they have many advantages in use.

The reaction between the various starting materials is very complex and,therefore, we cannot demonstrate with certainty the precise formula ofthe alkaline additives of our invention. We do, however, know that thecarbonyl group of the aldehyde reactant or ketone reactant is capable ofreacting with one or more of the several different reactive amino groupsavailable. The following equations show some of the possible reactionsand illustrate said complexity:

Equation (1) illustrates the reaction between .the secondary amino groupof the polyamine moiety and the carbonyl group of the aldehyde reactantor ketone reactant to form a cyclic group. Equation (2) illustrates thereaction between the primary amino group of the polyamine moiety and thecarbonyl group of the aldehyde reactant or ketone reactant to form animine group. Only one of these reactions may be dominating, but it ispossible that all occur simultaneously and at about the same rate.Because of the availability of so many different reactive amino groups,the amount of aldehyde and/or ketone reactants used may vary greatly.The only criterion is that the aldehyde and/or ketone reactants be addeduntil the condensation product is soluble in oil. In general,formaldehyde, polyamine, and the substituted phenol are reacted intherespective molar ratios of about l-2:l-2:l. When the formaldehyde,polyamine, and phenol are reacted in these relative proportions,generally from 1-4 moles of aldehyde and/or ketone reactant is employed.

Preferably, the aldehyde and ketone reactants have at least six carbonatoms. The greater number of carbon atoms in the aldehyde and ketonereactants and the greater the branching of the hydrocarbon chain ofthese reactants, the more oil-soluble the condensation product. Weespecially prefer those aldehyde and ketone reactants having branchedalkyl groups containing from six to 18 carbon atoms. Examples ofsuitable aldehyde reactants are: hexanal, heptanal, Z-rnethyl 1heptanal, 2-ethyl heptanal, 2-methyl-4-ethylheptanal, f 3-methyldecanal, 3,5-dimethyl decanal, 3'f-etl1yl-5-- methyl decanal, 5-butyldecanal', ,S-methyI-I 'Q -butyl decanal, S-methyl pentadecanal, S-ethylpentadecanal and 3-methyl heptadecanal. Examples. of suitable ketonereactants are: 2-hexanone, 3-heptanone, 3-octanone, 2-methyl-3-octanone,2-ethyl-3-octanone, 5- methyl-3-decanone, 5-ethyl-3-decanone,5-propyl-3- decanone, 5-propyl-3-undecanone, 5-penta-3- decanone,2-methyl-5-pentadecanone, 2-ethyl-5-pentadecanone, and 2-propyl-5-pentadecanone.

The alkyl substituents of preferred alkyl-substituted phenols containless than about 40 carbon atoms, and most preferably contain branchedalkyl groups from about one to about 18 carbon atoms.

Suitable alkylene polyamines generally come within the followingformula: i

in which n is an integer from about 1 to about 10, and

preferred alkylene polyamines are ethylene polyamines (alkylene havingtwo carbon atoms) of which tetraethylene pentamine is the mostpreferred. Other alkylene polyamines include, for example, propylenepolyamines, butylene polyamines, and cyclic homologues of suchpolyamines, for example piperazines. Specific examples of still otheralkylene polyamines are: ethylene diamine, diethylene triamine,

pentaethylene tetramine, and N-Z-aminoethylpiperazine.

PREPARATION OF MANNICH CONDENSATION PRODUCT Mix 5 moles of p-nonylphenoland moles of tetraethylene pentamine in a suitable flask fitted withstirring apparatus, reflux condenser, a Barrett trap, and a nitrogeninlet tube. Then, with stirring, slowly add to the flask over a periodof about 2 hours 10 moles of formaldehyde dissolved in water (63 weightpercent water). As formaldehyde is added, the temperature of thereaction mixture rises from ambient to about 70 C. When all theformaldehyde is added, stop stirring, inject nitrogen into the reactionmixture as an aid in removing water, and heat for several hours (about36), gradually increasing temperature from 70 to 160 C to remove thewater added with the formaldehyde and the water formed during thecondensation reaction. The water collects in the Barrett trap. A Mannichcondensation product so prepared has an average molecular weight ofabout 557.

DESCRIPTION OF THE PREFERRED EMBODIMENTS EXAMPLE I Dissolve 1.8 moles ofMannich product in 500 milliliters of isopropyl alcohol contained in asuitable flask fitted with a reflux condenser, stirring apparatus, aBarrett trap, and a nitrogen inlet tube. With stirring. slowly add tothe flask over a period about 1 hour 3 moles of a mixture of branchedchain aldehydes containing 10 carbon atoms (Enjay Chemical Co. MD-223).As this mixture of aldehydes is added, the temperature of the reactionwill rise from ambient to about 55 C. When all the aldehyde is added,inject nitrogen into the reaction mixture, and heat the mixture forseveral hours (about 36), gradually increasing the temperature from 55to 170 C to remove the alcohol and by-product water. An alkalineadditive so prepared has a molecular weight of about 600, and is readilydispersed in SAE-SW oil. To make this additive even more oil-soluble, itis reacted with more aldehydes as described in Example 11.

EXAMPLE II In a suitable flask, mix 1.2 moles of the alkaline additivemade in Example I with 700 grams of SAE-SW oil. Then, with stirring,slowly .add to the mixture over a period of about 35 minutes 0.9 mole ofthe mixture of C aldehydes. As the aldehyde is added, the temperature ofthe reaction mixture rises from ambient to about 36 C. Cover the mixturewith nitrogen and heat at 150 C for about 2 hours, and then cool. Thealkaline additive thus prepared is a bright amber oily material which issoluble in hot oil.

EXAMPLE III Dissolve 1.8 moles of Mannich product in 500 grams of SAE-SWoil contained in a suitable flask fitted with the necessary stirring,reflux, and nitrogen feed equipment. Inject nitrogen into the flask andslowly, with stirring, add to the flask over a period of about 1 hour 4moles of the mixture of C aldehydes. Then heat for several hours whileinjecting nitrogen. An alkaline additive so prepared is soluble in hotoil.

EXAMPLE IV In a suitable flask fitted with suitable equipment, mix 1mole of Mannich product with 500 grams of SAE-SW oil, and then add 2moles of hexanal and 2 moles of 2-methyl-3-octanone. Heat the reactionmixture for several hours and inject nitrogen to remove water. Analkaline additive so prepared is oil-soluble.

The above examples have been presented merely to illustrate thepreferred embodiments of our invention. Those skilled in the art willimmediately appreciate that these examples can be changed in manydetails. For example, other aldehydes, ketones, and Mannich productscoming within the scope of our disclosure will react similarly to thoseillustrated in the examples.

We claim:

1. The reaction product of (a) formaldehye; (b) an alkylene polyaminehaving the formula: H,N(alkyleneNH),,H in which n is an integer from 1to 10 and alkylene has from two to eight carbon atoms; (c) analkyl-substituted phenol wherein the alkyl group has less than 40 carbonatoms; and (d) an aldehyde reactant or a ketone reactant, or a mixtureof said aldehyde reactant and ketone reactant, said adehyde reactantand/or ketone reactant having from six to 18 carbon atoms, saidformaledhyde, polyamine and substituted phenol being reacted at atemperature of from about C to about 200 C in the respective molarratios of about l2:l-221, and said aldehyde reactant and/or ketonereactant being reacted in an amount sufficient to impart oil solubilityto the product at a temperature of from about 100 C to about 200 C.

2. The condensation product defined in claim 1 wherein the formaldehyde,polyamine, substituted phenol and the aldehyde reactant and/or ketonereactant are reacted in the respective molar ratios of about l2:l4.

3. The composition defined in claim 2 wherein the alkyl substituent ofthe alkyl-substituted phenol contains from one to 18 carbon atoms.

2. The condensation product defined in claim 1 wherein the formaldehyde,polyamine, substituted phenol and the aldehyde reactant and/or ketonereactant are reacted in the respective molar ratios of about1-2:1-2:1:1-4.
 3. The composition defined in claim 2 wherein the alkylsubstituent of the alkyl-substituted phenol contains from one to 18carbon atoms.